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  • 1
    Electronic Resource
    Electronic Resource
    Proximate, syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry (2000)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 763-785 
    Details
    ISSN: 1434-193X
    Keywords: Bisdiazenes ; Homoconjugation ; Photochemistry ; Heterocycles ; Diazenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Rigid N=N/N=N (diazene/diazene) systems (F) consisting of more or less alkylated DBH and DBO chromophoric units (1, 2, X-ray structures), with very short π,π distances [d = 2.849 (1a, av.), 2.822 Å (2)] and almost perfect syn-periplanar π,π alignments [ω = 168.6 (1a), 174.2° (2)] as well as the more flexible, less “proximate” metathesis isomers (3a,c, 27a,c, d 〉4.6 Å, ω = 90-100°) have been synthesized. Homoconjugate π,π interaction (in 1, 2, not in 3, 27) is deduced from UV spectroscopic measurements [π → π* maxima at 239 (234) nm (sh, 260)], while PE analyses furnished only small interaction parameters (1a: 〈0.3 eV). The potential of the novel syn-periplanar N=N/N=N motif in 1 and 2 for the synthesis of somewhat exotic polyheterocycles has been explored by calculation (B3LYP) as well as experimentally: i.a. kinetically stabilized, all-cis-peralkylated tetrazolidines (38, 44) and perhydro-1,2,4,5-tetrazines (41, 47) have become accessible (i.a. via novel azomethine/diazene and azomethine/azomethine cycloadditions). In 1a with its unreactive DBO chromophoric subunits, in the “buttressed” derivatives 1b-d, as well as in the DBH/DBO combination 2, and likewise in more ‘distant’ 27 (differently from the analogous C=C/C=C and N=N/C=C systems), irrespective of the excitation conditions employed (light of λ ≥≥ 280, 254 nm, low temperature matrix irradiation, acetone sensitization) no [2+2]photocycloaddition was observed. Instead exclusively N2-elimination took place. It is argued that unproductive N=N/N=N photocycloaddition would have become observable through metathesis isomerization of the respective tetrazetidines.
    Additional Material: 9 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Proximate, syn-Periplanar, Rigid Imine(Nitrone)/Ene-, and Diazene(Diazeneoxy)/Ene Systems: Syntheses, Homoconjugate Reactivity and Photochemistry (2000)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 743-762 
    Details
    ISSN: 1434-193X
    Keywords: Chromophores ; Photochemistry ; Heterocycles ; Diazenes ; Imines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The chances for intramolecular imine/ene (→ azetidines), diazene/ene (→ 1,2-diazetidines), diazeneoxy/ene (→ 1,2-diazetidine oxides) and diazenedioxiene (→ 1,2-diazetidine dioxides) [2+2]photocycloadditions and for the isolation of the respective photoproducts, have been probed with specifically designed substrates. Upon direct or sensitized excitation, [2+2]cycloaddition was found to be the exclusive or at least dominant chemical process for the C=N/C=C, N=N/C=C and ON=N(O)/C=C systems featuring very small π,π-distances of 2.8-3.0 Å and large π,π-interorbital angles of 160-170° (7 → 51, 17 → 55, 33 → 58 (competing N2 elimination), 22 → 62). This is not the case, however, in ON=NO/C=C (23, where electron transfer is a possibility), or in the more flexible, less “proximate” C=N/C=N (57) and C=NO/C=N (63) systems (π,π-distances of 〉3.8 Å). While the corseted 1,2-diazetidine photoadducts (55, 58) proved to be thermally stable, their N-oxides (62, 65) were thermally too labile to be directly observable above -65 °C. For the latter's only fleeting existence, electronic rather than strain effects are held responsible (B3LYP/6-31G* calculations). Very facile C=NO/C=C (12 → 13) and N=NO/C=C (22 → 24) [3+2]cycloadditions, homoconjugate addition of H2 and of dienophiles ([2+2+2]) to the diazene/ene 17 (→ 39, 41, 45) are manifestations of “proximity” in these bichromophoric skeletons.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Proximate, syn-Periplanar Diazene/Diazene(di)oxy, Diazeneoxy/Diazene(di)oxy, and Diazenedioxy/Diazenedioxy Skeletons: Syntheses, [2+2]Photocycloadditions, Metathesis (2000)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 787-806 
    Details
    ISSN: 1434-193X
    Keywords: Photochemistry ; Heterocycles ; Diazenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Of two very proximate syn-periplanar bisdiazenes (1,2) mono-, di-, tri- and tetra-N-oxides were prepared, representing six combinations of the individual N=N/N=NO/ON=NO chromophores. According to DFT calculations (B3LYP/6-31G*), [2+2]photocycloaddition to the respective oxidized tetrazetidines is significantly to moderately endothermic. The metathesis isomerization of the oxidized tetrazetidines is generally highly exothermic and kinetically increasingly favorable with increasing oxidation state. In practice, four out of the six bichromophoric combinations undergo selectively, in competition with N2 elimination from a DBH unit (13) still partially, metathesis isomerization upon π → π* excitation (monochromatic 254 nm light). In the case of the syn-N=NO/N=NO combinations (5/6, 14), the photoaddition is thermally reversed. For a ON=NO/N=N combination (30), internal electron transfer is responsible for a complex reaction pattern. The preparative value of the metathesis reactions, though, is limited: The metathesis-derived bis[diazene mono(di)oxides] undergo relatively fast secondary photoreactions, while the tri(tetra)oxides undergo rapid thermal transformations. For the N=N/N=NO systems (12), of three potential pathways for its metathesis isomerization, the one that takes place via σ-symmetric intermediates (63, 64) is excluded by virtue of the retention of optical purity in the photometathesis of a highly enriched enantiomer [(-)-12]. Matrix irradiation experiments (12 K, IR control) with 12 result in the appearance of a kinetically highly labile transient. Supported by DFT calculations it is concluded that in the metathesis reactions, the respective tetrazetidine oxides (increasingly destabilized by interactions between oxygen lone pairs and NNσ* orbitals) function as vibrationally excited transients. That thermal reversion of these transients might be a general, nonproductive competition, is suggested by the experimental verification of a “reversed photometathesis” (51 → 15) and by the generally low rates in product formation upon irradiation. The question remains to be answered why in structurally analogous molecular skeletons, [2+2]photocycloaddition occurs in the C=C/N=N and variously oxidized N=N/N=N, and not, however, in the parent N=N/N=N combinations.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. 33 [1] 2-Dialkylamino-2H-thiopyrane aus 2,4,6-Triaryl-thiopyryliumsalzen (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 567-572 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. 33. 2-Dialkylamino-2H-thiopyrans from 2,4,6-Triaryl-thiopyrylium Salts2,4,6-Triaryl-thiopyrylium salts 7 react with dialkylamines in diethyl ether to give stable crystalline 2-dialkylamino-2H-thiopyrans 8, the structure of which is in accordance with their u.v., n.m.r. and mass spectra. The chemical properties of 8 parallel those of structurally analogous 2-alkoxy- and 2-dialkylamino-2H-pyrans and 2-alkoxy-2H-thiopyrans. Thus, on heating 2-dimethylamino-2,4,6-triphenyl-2H-thiopyran (8a) with methanol the corresponding 2-methoxy-2H-thiopyran 9 is formed. Nitromethane and ethyl cyanoacetate give rise to ring transformations yielding 1,3,5-triphenyl benzene (10) and 2,4,6-benzonitrile (11), respectively. From 8a electrophiles (e.g. mineral acids, methyl iodide, benzoyl chloride) regenerate the initial thiopyrylium system by taking over the dialkylamino group.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280416
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  • 5
    Electronic Resource
    Electronic Resource
    Organische Phosphorverbindungen. XV [1] Reaktivitätsuntersuchungen an ausgewählten Vinylphosphaten (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 651-655 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Phosphorus Compounds. XV. Studies on the Reactivity of Selected Vinyl Phosphates
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280429
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  • 6
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen, XXVI. Vergleichende UV/Vis-spektroskopische Untersuchungen an 3-Methyl-2,4,6-triaryl-pyrylium-perchloraten (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 151-155 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXVI. Comparative U.V./Vis. Studies on 3-Methyl-2,4,6-triarylpyrylium Perchlorates
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270122
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  • 7
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. XVIII, 2-Alkoxy-2H-pyrane aus tetra- und pentasubstituierten Pyryliumsalzen (1983)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 325 (1983), S. 729-741 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XVIII. 2-Alkoxy-2H-pyrans from Tetra- and Pentasubstituted Pyrylium SaltsAlkali alkoxides add regioselectively to 2,3,4,6-tetrasubstituted pyrylium salts 7 (R'= H), affording high yields of colourless crystalline 2-alkoxy-2H-pyrans 9. The latte are also formed simply on refluxing 7 in the corresponding alcohol with triethylamine as proton acceptor. 3,5-Dialkylsubstituted 2,4,6-triarylpyrylium salts react analogously. The 2H-pyran structure of the adducts obtained follows from their n.m.r., i.r., u.v. and mass spectra as well as from their reaction with tetracyanoethylene to cycloadducts of type 10. Acids regenerate from 9 the original pyrylium cations, whereas reaction of 9 with nitromethane or ethyl cyanoacetate provides benzene derivatives. -- The novel starting pyrylium salts 7b--o are characterized by u.v./vis data and by transformation into the corresponding pyridine derivatives
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19833250507
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  • 8
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. XXVII. Spezifisch deuterierte Carbo- und Heterocyclen via 2,4,6-Triaryl-[3,5-2H2]pyryliumsalze (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 529-535 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXVIII. Specifically Deuterated Carbo- and heterocycles via 2,4,6-Triaryl[3,5-2H2]pyrylium SaltsOn heating with catalytic amounts of bases(e.g. triethyl amine) in deuterated alcohols such as methan[2H]ol or ethan[2H]ol pseudobases of 2, 4, 6-triarylpyrylium salts 1 undergo fast1H/2H isotopic exchange reaction affording 1, 3, 5-triaryl[2, 4, 4-2H3]pent-2-ene-1,5-diones which with [2H] perchloric acid give highly deuterated 2, 4, 6-triaryl-[3, 5-2H] pyrylium perchlorates 8. These salts are obtainable also directly from 1 through a one-pot procedure by ring opening of the latter with deuterium oxide under the above-mentioned1H/2H isotopic exchange conditions followed by recyclization of the formed 1, 3, 5-triaryl[2, 4, 4-2H3]pent-2-ene-1, 5-diones with [2H]ClO4. Ring transformations of 2, 4, 6-triphenyl[3, 5-2H2]pyrylium perchlorate (8a) to 2, 4, 6-triphenyl[3, 5-2H2]nitrobenzene (9) 2, 4, 6-triphenyl[3, 5-2H2]pyridine (10), 1, 2, 4, 6-tetraphenyl[3, 5-2H2]pyrydinium perchlorate(11), 2, 4, 6-triphencyl[3, 5-2H2]thiopyrylium perchlorate(12), 2-benzoyl-3, 5-diphenyl[4-2H]furan (13), and 3, 5, 7-triphenyl-[4, 4, 6-2H3]4H-1, 2-diazepin (14) demonstrate the usability of pyrylium salts of type 8 as starting materials for syntheses of specifically deuterated carbo- and hetrocycles.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270402
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  • 9
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen. 36. Substituierte Benzoesäureester aus 2,4,6-Triaryl-pyryliumsalzen und α-Ketocarbonsäureestern (1987)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 329 (1987), S. 499-510 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. 36. Substituted Benzoic Acid Esters from 2,4,6-Triarylpyrylium Salts and α-Ketocarboxylic Acid Esters2,4,6-Triarylpyrylium salts 1 react with α-ketocarboxylic acid esters 2 in the presence of two equivalents of an appropriate condensing agent (e.g. dialkylamine salts of weak acids, triethylamine/acetic acid, or sodium acetate) to give 2-aroyl-3,5-diarylbenzoic acid esters 3. However, using only one equivalent of the condensing agent, the formation of 3,5-diarylbenzoic acid esters 5 predominates. Alkaline saponification of the new esters 3 and 5 yields the corresponding substituted benzoic acids 4 and 6, respectively. - I.r., u.v., n.m.r. and mass spectroscopic data of the novel products 3-6 are reported.
    Additional Material: 9 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19873290317
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  • 10
    Electronic Resource
    Electronic Resource
    Pyryliumverbindungen, XXV. Quantenchemische Berechnungen zur Valenzisomerisierung von 2-Amino-2H-pyran und -thiopyran (1984)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 326 (1984), S. 955-961 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrylium Compounds. XXV. Quantum Chemical Calculations Concerning the Valence Isomerization of 2-Amino-2H-pyran and -thiopyranThe equilibrium 2-amino-2H-pyran 6 ⇌ 5-amino-2,4-dien-1-one 7 was investigated using the semi-empirical MINDO/3 and MNDO methods. In accordance with experimental findings for the substituted derivatives 1/2a-d, the introduction of a methyl group into the position 3 of 6 or the exchange of oxygen by sulfur shifts the equilibrium towards the cyclic structures 8 and 10, respectively. Polar solvents, the influence of which was estimated applying the reaction field approach as well as the solvaton theory, and entropy effects are calculated to favour the ring-open valence isomer 7. These results also correspond to experimental results.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19843260614
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